Microgel Colloidosomes Based on pH-Responsive Poly(<i>tert</i>-butylaminoethyl methacrylate) Latexes

Emulsion copolymerization of 2-(<i>tert</i>-butylamino)­ethyl methacrylate (TBAEMA) with divinylbenzene (DVB) cross-linker in the presence of monomethoxy-capped poly­(ethylene glycol) methacrylate (PEGMA) at 70 °C afforded sterically stabilized poly­[2-(<i>tert</i>-butylamino)­ethyl methacrylate] (PTBAEMA) latexes at 10% solids at pH 9. Such particles proved to be an effective Pickering emulsifier at pH 10 for both <i>n</i>-dodecane and <i>n</i>-hexane. ¹H NMR spectroscopy was used to follow the model reaction between the secondary amine of the TBAEMA monomer and the isocyanate groups of tolylene 2,4-diisocyanate-terminated poly­(propylene glycol) (PPG-TDI). Cross-linking the PTBAEMA latex particles adsorbed at the <i>n</i>-dodecane/water interface using this oil-soluble PPG-TDI cross-linker at around 0 ^oC led to robust colloidosomes that survived an acid challenge. This resistance to demulsification was confirmed via laser diffraction studies following an in situ switch from pH 10 to 3, since no change was observed in either the oil droplet size or concentration (compared to non-cross-linked PTBAEMA-stabilized Pickering emulsions). Such PTBAEMA colloidosomes survived removal of the internal oil phase on washing with excess ethanol. However, because ethanol is a good solvent for the PTBAEMA chains, imaging the ethanol-treated colloidosomes via electron microscopy proved rather problematic due to partial film formation. Therefore, a series of TBAEMA/styrene copolymer latexes (comprising 10, 30, 50, or 60 mol % styrene) were prepared via emulsion copolymerization at 70 °C in the presence of DVB and PEGMA. The higher glass transition temperatures exhibited by these copolymer particles (and their greater resistance to ethanol swelling) enabled better-quality electron microscopy images to be obtained. The presence of nitrogen atoms at the surface of these copolymer latex particles was confirmed via X-ray photoelectron spectroscopy studies; these secondary amine groups allow covalent cross-linking via PPG-TDI when adsorbed at the surface of <i>n-</i>dodecane droplets at TBAEMA comonomer contents as low as 40 mol %. After removal of the <i>n</i>-hexane oil phase by evaporation, fluorescence microscopy studies indicate that these colloidosomes undergo collapse in their latex form at pH 10 but regain their original spherical morphology in their cationic microgel form at pH 3.5